This invention relates to processes for the production of electrophoretic displays.
The term “electro-optic”, as applied to a material or a display, is used herein in its conventional meaning in the imaging art to refer to a material having first and second display states differing in at least one optical property, the material being changed from its first to its second display state by application of an electric field to the material. Although the optical property is typically color perceptible to the human eye, it may be another optical property, such as optical transmission, reflectance, luminescence or, in the case of displays intended for machine reading, pseudo-color in the sense of a change in reflectance of electromagnetic wavelengths outside the visible range.
The terms “bistable” and “bistability” are used herein in their conventional meaning in the art to refer to displays comprising display elements having first and second display states differing in at least one optical property, and such that after any given element has been driven, by means of an addressing pulse of finite duration, to assume either its first or second display state, after the addressing pulse has terminated, that state will persist for at least several times, for example at least four times, the minimum duration of the addressing pulse required to change the state of the display element. It is shown in U.S. Pat. No. 7,170,670 that some particle-based electrophoretic displays capable of gray scale are stable not only in their extreme black and white states but also in their intermediate gray states, and the same is true of some other types of electro-optic displays. This type of display is properly called “multi-stable” rather than bistable, although for convenience the term “bistable” may be used herein to cover both bistable and multi-stable displays.
Particle-based electrophoretic display, in which a plurality of charged particles move through a fluid under the influence of an electric field, have been the subject of intense research and development for a number of years. Electrophoretic displays can have attributes of good brightness and contrast, wide viewing angles, state bistability, and low power consumption when compared with liquid crystal displays. Nevertheless, problems with the long-term image quality of these displays have prevented their widespread usage. For example, particles that make up electrophoretic displays tend to settle, resulting in inadequate service-life for these displays.
As noted above, electrophoretic media require the presence of a fluid. In most prior art electrophoretic media, this fluid is a liquid, but electrophoretic media can be produced using gaseous fluids; see, for example, Kitamura, T., et al., “Electrical toner movement for electronic paper-like display”, IDW Japan, 2001, Paper HCS1-1, and Yamaguchi, Y., et al., “Toner display using insulative particles charged triboelectrically”, IDW Japan, 2001, Paper AMD4-4). See also U.S. Patent Publication No. 2005/0001810; European Patent Applications 1,462,847; 1,482,354; 1,484,635; 1,500,971; 1,501,194; 1,536,271; 1,542,067; 1,577,702; 1,577,703; and 1,598,694; and International Applications WO 2004/090626; WO 2004/079442; and WO 2004/001498. Such gas-based electrophoretic media appear to be susceptible to the same types of problems due to particle settling as liquid-based electrophoretic media, when the media are used in an orientation which permits such settling, for example in a sign where the medium is disposed in a vertical plane. Indeed, particle settling appears to be a more serious problem in gas-based electrophoretic media than in liquid-based ones, since the lower viscosity of gaseous suspending fluids as compared with liquid ones allows more rapid settling of the electrophoretic particles.
Numerous patents and applications assigned to or in the names of the Massachusetts Institute of Technology (MIT) and E Ink Corporation have recently been published describing encapsulated electrophoretic media. Such encapsulated media comprise numerous small capsules, each of which itself comprises an internal phase containing electrophoretically-mobile particles suspended in a liquid suspending medium, and a capsule wall surrounding the internal phase. Typically, the capsules are themselves held within a polymeric binder to form a coherent layer positioned between two electrodes. Encapsulated media of this type are described, for example, in U.S. Pat. Nos. 5,930,026; 5,961,804; 6,017,584; 6,067,185; 6,118,426; 6,120,588; 6,120,839; 6,124,851; 6,130,773; 6,130,774; 6,172,798; 6,177,921; 6,232,950; 6,249,271; 6,252,564; 6,262,706; 6,262,833; 6,300,932; 6,312,304; 6,312,971; 6,323,989; 6,327,072; 6,376,828; 6,377,387; 6,392,785; 6,392,786; 6,413,790; 6,422,687; 6,445,374; 6,445,489; 6,459,418; 6,473,072; 6,480,182; 6,498,114; 6,504,524; 6,506,438; 6,512,354; 6,515,649; 6,518,949; 6,521,489; 6,531,997; 6,535,197; 6,538,801; 6,545,291; 6,580,545; 6,639,578; 6,652,075; 6,657,772; 6,664,944; 6,680,725; 6,683,333; 6,704,133; 6,710,540; 6,721,083; 6,724,519; 6,727,881; 6,738,050; 6,750,473; 6,753,999; 6,816,147; 6,819,471; 6,822,782; 6,825,068; 6,825,829; 6,825,970; 6,831,769; 6,839,158; 6,842,167; 6,842,279; 6,842,657; 6,864,875; 6,865,010; 6,866,760; 6,870,661; 6,900,851; 6,922,276; 6,950,200; 6,958,848; 6,967,640; 6,982,178; 6,987,603; 6,995,550; 7,002,728; 7,012,600; 7,012,735; 7,023,420; 7,030,412; 7,030,854; 7,034,783; 7,038,655; 7,061,663; 7,071,913; 7,075,502; 7,075,703; 7,079,305; 7,106,296; 7,109,968; 7,110,163; 7,110,164; 7,116,318; 7,116,466; 7,119,759; 7,119,772; 7,148,128; 7,167,155; 7,170,670; 7,173,752; 7,176,880; 7,180,649; 7,190,008; 7,193,625; 7,202,847; 7,202,991; 7,206,119; 7,223,672; 7,230,750; 7,230,751; 7,236,790; and 7,236,792; and U.S. Patent Applications Publication Nos. 2002/0060321; 2002/0090980; 2003/0011560; 2003/0102858; 2003/0151702; 2003/0222315; 2004/0094422; 2004/0105036; 2004/0112750; 2004/0119681; 2004/0136048; 2004/0155857; 2004/0180476; 2004/0190114; 2004/0196215; 2004/0226820; 2004/0257635; 2004/0263947; 2005/0000813; 2005/0007336; 2005/0012980; 2005/0017944; 2005/0018273; 2005/0024353; 2005/0062714; 2005/0067656; 2005/0099672; 2005/0122284; 2005/0122306; 2005/0122563; 2005/0134554; 2005/0151709; 2005/0152018; 2005/0156340; 2005/0179642; 2005/0190137; 2005/0212747; 2005/0213191; 2005/0219184; 2005/0253777; 2005/0280626; 2006/0007527; 2006/0024437; 2006/0038772; 2006/0139308; 2006/0139310; 2006/0139311; 2006/0176267; 2006/0181492; 2006/0181504; 2006/0194619; 2006/0197736; 2006/0197737; 2006/0197738; 2006/0202949; 2006/0223282; 2006/0232531; 2006/0245038; 2006/0256425; 2006/0262060; 2006/0279527; 2006/0291034; 2007/0035532; 2007/0035808; 2007/0052757; 2007/0057908; 2007/0069247; 2007/0085818; 2007/0091417; 2007/0091418; 2007/0097489; 2007/0109219; 2007/0128352; and 2007/0146310; and International Applications Publication Nos. WO 00/38000; WO 00/36560; WO 00/67110; and WO 01/07961; and European Patents Nos. 1,099,207 B1; and 1,145,072 B1.
Although electrophoretic media are often opaque (since, for example, in many electrophoretic media, the particles substantially block transmission of visible light through the display) and operate in a reflective mode, many electrophoretic displays can be made to operate in a so-called “shutter mode” in which one display state is substantially opaque and one is light-transmissive. See, for example, the aforementioned U.S. Pat. Nos. 6,130,774 and 6,172,798, and U.S. Pat. Nos. 5,872,552; 6,144,361; 6,271,823; 6,225,971; and 6,184,856. Dielectrophoretic displays, which are similar to electrophoretic displays but rely upon variations in electric field strength, can operate in a similar mode; see U.S. Pat. No. 4,418,346.
An encapsulated electrophoretic display typically does not suffer from the clustering and settling failure mode of traditional electrophoretic devices and provides further advantages, such as the ability to print or coat the display on a wide variety of flexible and rigid substrates. (Use of the word “printing” is intended to include all forms of printing and coating, including, but without limitation: pre-metered coatings such as patch die coating, slot or extrusion coating, slide or cascade coating, curtain coating; roll coating such as knife over roll coating, forward and reverse roll coating; gravure coating; dip coating; spray coating; meniscus coating; spin coating; brush coating; air knife coating; silk screen printing processes; electrostatic printing processes; thermal printing processes; ink jet printing processes; electrophoretic deposition (see US Patent Publication No. 2004/0226820); and other similar techniques.) Thus, the resulting display can be flexible. Further, because the display medium can be printed (using a variety of methods), the display itself can be made inexpensively.
One major reason why encapsulated electrophoretic displays can be produced inexpensively by printing processes is that the electrophoretic medium itself has substantial mechanical strength and cohesion; typically the individual capsules are bound together by a polymeric binder to increase the cohesion of the layer. Thus, not only can the display medium itself be printed, but as described in U.S. Pat. No. 6,177,921, an electrode may be formed by printing a conductive material directly on to the electrophoretic medium; alternatively, an electrode pre-formed on a substrate can be laminated on to the electrophoretic medium, which is able to withstand the heat and pressure required for such lamination without damage. In such printed or laminated structures, the mechanical strength and cohesion of the electrophoretic medium maintain the requisite spacing between the electrodes disposed on either side of the medium without any need for mechanical spacers or similar devices to control this spacing. Accordingly, if the electrodes (and any substrates attached thereto) are flexible, the encapsulated electrophoretic display can be curved or rolled without affecting the display qualities of the device; see, for example, Drzaic et al., A Printed and Rollable Bistable Electronic Display SID (Society for Information Display) 98 Digest, page 1131 (1998), which illustrates a flexible encapsulated electrophoretic display being rolled around a pencil without damage.
Furthermore, because of the mechanical strength and cohesion of the electrophoretic medium, such a medium can in principle be applied to any substrate on which an electrode can be provided; for example, the substrate could have an arbitrary three-dimensional shape, as opposed to an essentially laminar sheet which is curved in one dimension. Techniques such as sputtering may be used to apply electrodes to arbitrary three-dimensional shapes, but prior art techniques for applying an electrophoretic medium to such arbitrary shapes leave a great deal to be desired, especially given the need for careful control of the deposition of such a medium to produce optimum optical performance.
Display performance (e.g., its optical performance) and visual appeal (i.e., minimizing visual defects) depends critically on obtaining a high quality coating, that is coatings are preferably of uniform thickness (often a monolayer of capsules is desirable), and contain a high areal density of capsules with a minimum of defects. For example, regions where capsules are not in contact with the electrode or where the surface density of capsules varies laterally with respect to the substrate, or where the coating thickness varies, show up as a degraded dark or white states, non-uniformity in the optical state or graininess, or as non-uniformities during switching respectively.
Some of the printing/coating techniques described above can produce high quality printings/coatings of capsules on to planar or flexible substrates; during coating, flexible substrates are usually constrained so that at least one of the radii of curvature of the substrate is infinite, i.e., the substrate is held in a cylindrical form with the axis of the cylinder perpendicular to the direction of coating. In particular, certain of the aforementioned E Ink and MIT patents and applications describe the use of a metered slot coating technique to produce monolayer capsule coatings and lamination adhesive coatings suitable for use in commercial products.
However, as already mentioned these prior art techniques are not satisfactory for forming, on arbitrary three-dimensional shapes, electrophoretic medium coatings with a sufficiently uniform thickness to give optimum optical performance. While coating methods such as dip or spray coating can be applied to arbitrary three-dimensional shapes, it is difficult to or impossible to achieve uniform capsule monolayers over the substrate surface using these coating techniques.
Other problems encountered with slot coating techniques include:                (a) chatter-like streaks parallel to the coating head (for example, due to vibrations in the coating apparatus); these streaks are believed to result from periodic bunching or jamming of capsules;        (b) streaking in the direction of coating (i.e., perpendicular to the slot of the coating head), believed to be due to capsule jamming or non-uniform flows in delivery of capsules to the coating head;        (c) less than desirable capsule contact (or wetting) with the optical face due to inadequate settling or deformability of the small capsules (of the order of 20-200 μm) typically used in encapsulated electrophoretic displays; and        (d) non-uniformities in coating thickness due to formation of multiple layers of capsules (see the aforementioned U.S. Pat. No. 6,839,158 for a discussion of the advantages of forming only a single layer of capsules on a substrate).The presence of these types of defects can adversely affect the appearance and optical performance of the display.        
Also, as is well known to those skilled in slot coating technology, slot coating imposes limitations upon the viscosity and other physical properties of the material being coated, and typically requires the addition of slot coating additives to control the rheology of the coated material to ensure that the coating does not flow and develop non-uniformities in thickness prior to drying. As discussed in many of the aforementioned E Ink and MIT patents and applications, typically the capsules are mixed with a polymeric binder prior to coating, this polymeric binder serving to form the capsules into a coherent layer after coating and drying. The capsule/binder mixture is then coated on to a polymeric film substrate bearing a conductive coating of indium tin oxide (ITO) or a conductive polymer and dried to form a coherent layer on the conductive-coating bearing surface of the substrate; the opposed surface of the substrate forms the viewing surface of the final display. Although the binder serves several useful functions, including ensuring adequate adhesion of the capsule film to the substrate on which it is coated, excessive amounts of binder can hinder capsule contact with the electrode which is normally present on the substrate, and may also hinder the desirable flattening of the faces of the capsules in contact with the conductive coating (see, for example, the aforementioned U.S. Pat. No. 6,067,185). Because the binder typically has a substantial effect on the viscosity and other physical properties of the capsule/binder mixture, at least in some cases it may be difficult to reduce the amount of binder used and still maintain these physical properties at values compatible with slot coating.
Also, some of the aforementioned E Ink and MIT patents and applications (see especially 2002/0113770) describe displays in which more than one type of capsule is used, the plurality of types of capsules being arranged in a predetermined pattern on a substrate. For example, a full color display could make use of three different types of capsules, say white/red, white/green and white/blue arranged in stripes of triads; such a display could achieve full color without requiring a color filter of the type used in full color liquid crystal displays. However, while conventional printing techniques might be used to prepare large displays of this type having resolutions of (say) less than 10 lines per inch (approximately 0.4 lines per mm), producing high resolution displays of this type with resolutions of about 100 lines per inch (approximately 4 lines per mm) with such conventional techniques is very difficult. Again, while spray or ink jet coating might be used to apply the patterned coatings of capsules, producing monolayer capsule coatings using these methods will be difficult or impossible.
Improved methods for achieving patterned deposition of encapsulated electrophoretic media would facilitate several applications of electrophoretic displays that are presently difficult or impossible to achieve. Also, improved patterned deposition of electrophoretic media could improve the properties of several kinds of displays presently made by other processes. For example, spot-color displays can be made by superposing a colored film on top of a monochrome (black and white) display. If the backplane driving the display is appropriately segmented and connected to appropriate electronics, the part of the monochrome display under the colored film can be driven separately from the rest of the display so as to produce an area of color in addition to monochrome information. The colored film must be registered with the backplane, and the displayed color can only be that of the film, plus black. Switching between two colors (red plus blue, for example) is not possible in this type of display. Patterned electrophoretic medium deposition would allow deposition of media of arbitrary colors and color combinations. Media deposition registered with backplane segments would obviate the registration step, and could be used to provide high resolution flexible color applications.
Full color displays require separate addressing of (typically) three or four differently colored sub-pixels. Most prior art full color electrophoretic displays have used a registered color filter array superposed on a monochrome display driven by an active matrix backplane. An alternative way of achieving a full color electrophoretic display would be to use the same backplane with a patterned array of electrophoretic media containing appropriate sets of electrophoretic particles (most commonly, red plus black, green plus black, blue plus black, and optionally white plus black). Using multiple electrophoretic media in this way has several advantages in the construction of highly flexible full color displays, including avoiding difficulties in registration, especially registration when the display is flexed.
The present invention seeks to provide processes for the production of electrophoretic displays, and in particular for processes for depositing capsules on a substrate, which reduce or eliminate the problems of the prior art processes for depositing capsules described above. Some processes of the present invention can be used to produce full color displays. The present invention also provides apparatus for use in this process.